JP3200912B2 - 3D model manufacturing method - Google Patents
3D model manufacturing methodInfo
- Publication number
- JP3200912B2 JP3200912B2 JP01903392A JP1903392A JP3200912B2 JP 3200912 B2 JP3200912 B2 JP 3200912B2 JP 01903392 A JP01903392 A JP 01903392A JP 1903392 A JP1903392 A JP 1903392A JP 3200912 B2 JP3200912 B2 JP 3200912B2
- Authority
- JP
- Japan
- Prior art keywords
- photocurable resin
- resin composition
- colored
- resin
- photopolymerization initiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は立体モデルの製造方法に
関し、さらに詳しくは内部構造を明瞭にみてとることが
できる立体モデルの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a three-dimensional model, and more particularly to a method of manufacturing a three-dimensional model capable of clearly observing the internal structure.
【０００２】[0002]
【従来の技術】従来、立体モデルの製造には、紫外レー
ザ発振器、該レーザから出力されるレーザ光を光硬化性
樹脂に導く光学系、および三次元ＣＡＤ（Ｃｏｍｐｕｔ
ｅｒＡｉｄｅｄ Ｄｅｓｉｇｎ）データによる二次元像
を該光硬化性樹脂上にレーザ露光し、硬化部を移動させ
るコンピューター制御部からなる三次元立体モデルの製
造装置が使用されてきている。2. Description of the Related Art Conventionally, to produce a three-dimensional model, an ultraviolet laser oscillator, an optical system for guiding a laser beam output from the laser to a photocurable resin, and a three-dimensional CAD (Computing) have been proposed.
2. Description of the Related Art A three-dimensional three-dimensional model manufacturing apparatus including a computer control unit that exposes a two-dimensional image based on erAided Design data to a laser beam on the photocurable resin and moves a hardened part has been used.
【０００３】上記装置により製造される立体モデルは半
透明性を有するため、他の粘土や木からなる立体モデル
に比べ、外見のみならず内部構造も可視化されている。[0003] Since the three-dimensional model manufactured by the above-mentioned apparatus has translucency, not only the appearance but also the internal structure is visualized as compared with other three-dimensional models made of clay or wood.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、前記従
来の立体モデルは、半透明ではあるが単色のものである
ため、とくに立体モデルの内部構造が複雑である場合、
または内部の様子を正確に把握する必要のある場合、そ
の形状等を外部から識別できないという欠点があり、こ
のような問題についての速やかな解決が望まれていた。However, since the conventional three-dimensional model is translucent, but monochromatic, the above-mentioned three-dimensional model is particularly difficult when the internal structure of the three-dimensional model is complicated.
Alternatively, when it is necessary to accurately grasp the state of the inside, there is a disadvantage that the shape or the like cannot be identified from the outside, and a prompt solution to such a problem has been desired.
【０００５】[0005]
【課題を解決するための手段】本発明者は、かかる実情
に鑑み鋭意検討した結果、光照射波長により選択的に硬
化および着色しうる機能を樹脂に付与することにより内
部構造を識別可能な立体モデルが得られることを見出
し、本発明を完成するに至った。The inventor of the present invention has made intensive studies in view of the above circumstances, and as a result, it has been found that a resin capable of selectively hardening and coloring by a light irradiation wavelength is imparted to a resin so that the internal structure can be identified. They found that a model could be obtained and completed the present invention.
【０００６】すなわち、本発明は、少なくとも二つの異
なる吸収波長を有する一種の光重合開始剤と、光硬化性
樹脂と、光重合開始剤ではない着色剤とを含有する光硬
化性樹脂組成物を用い、 （ｉ）該光重合開始剤と該着色剤とに共通する吸収波長
の光を該光硬化性樹脂組成物の選択領域に照射して該光
硬化性樹脂組成物の該選択領域を硬化および着色する工
程と、 （ｉｉ）該光重合開始剤の吸収波長であって該着色剤の
吸収波長でない波長の光を該光硬化性樹脂組成物に照射
して、該光硬化性樹脂組成物を硬化するが着色しない工
程とを含むことを特徴とする、一部が着色された立体モ
デルの製造方法を提供するものである。That is, the present invention provides a photocurable resin composition containing at least two kinds of photopolymerization initiators having different absorption wavelengths, a photocurable resin, and a coloring agent that is not a photopolymerization initiator. (I) curing a selected area of the photocurable resin composition by irradiating a selected area of the photocurable resin composition with light having an absorption wavelength common to the photopolymerization initiator and the colorant; And (ii) irradiating the photocurable resin composition with light having a wavelength that is the absorption wavelength of the photopolymerization initiator but is not the absorption wavelength of the colorant, and the photocurable resin composition And a method of producing a partially colored three-dimensional model.
【０００７】本発明は、さらに、少なくとも二種の光硬
化性樹脂と、該光硬化性樹脂にそれぞれ対応しそして互
いに異なる吸収波長を有する少なくとも二種の光重合開
始剤とを含有する光硬化性樹脂組成物であって、該光硬
化性樹脂の少なくとも一種が硬化の際着色または変色す
る光硬化性樹脂であり、少なくとも一種が硬化の際着色
も変色もしない光硬化性樹脂である該光硬化性樹脂組成
物を用い、 （ｉ）該硬化の際着色または変色する光硬化性樹脂に対
応する光重合開始剤の吸収波長の光を該光硬化性樹脂組
成物の選択領域に照射して該樹脂組成物の該選択領域を
硬化および着色または変色させる工程と、 （ｉｉ）該硬化の際着色も変色もしない光硬化性樹脂に
対応する光重合開始剤の吸収波長の光を該光硬化性樹脂
組成物に照射して、該光硬化性樹脂組成物を硬化するが
着色しない工程とを含むことを特徴とする、一部が着色
または変色された立体モデルの製造方法を提供するもの
である。The present invention further provides a photocurable resin containing at least two photocurable resins and at least two photopolymerization initiators respectively corresponding to the photocurable resins and having mutually different absorption wavelengths. A resin composition, wherein at least one of the photo-curable resins is a photo-curable resin that is colored or discolored when cured, and at least one is a photo-curable resin that is not colored or discolored when cured. (I) irradiating a selected region of the photocurable resin composition with light having an absorption wavelength of a photopolymerization initiator corresponding to the photocurable resin which is colored or discolored during the curing. Curing and coloring or discoloring the selected area of the resin composition; and (ii) converting the light having the absorption wavelength of the photopolymerization initiator corresponding to the photocurable resin that does not discolor or discolor during the curing to the photocurable resin. Irradiate the resin composition Curing the photocurable resin composition is characterized in that it comprises a step which is not colored, in which a portion to provide a method for producing colored or discolored stereoscopic model.
【０００８】本発明に使用される混合樹脂（二種以上の
光硬化性樹脂を使用する場合）のうち少なくとも一種
は、光照射により硬化する性質を有し、かつ、光照射部
がその波長により選択的に照射前の樹脂色から別の色へ
と着色または変色する機能を有するものである。[0008] At least one of the mixed resins used in the present invention (when two or more kinds of photocurable resins are used) has a property of being cured by light irradiation, and the light irradiation part has a property depending on the wavelength. It has a function of selectively coloring or discoloring from a resin color before irradiation to another color.
【０００９】本発明に使用する樹脂の光硬化の際、同時
に該樹脂を着色または変色可能とするには、光硬化性樹
脂に下記（イ）および（ロ）に示す着色剤を添加した
り、または下記（ハ）に示すように樹脂自体に着色また
は変色機能を付与すればよい。In order to simultaneously color or change the color of the resin used in the present invention, it is possible to add the following colorants (A) and (B) to the photocurable resin. Alternatively, a coloring or discoloring function may be imparted to the resin itself as shown in (c) below.
【００１０】ここで、着色剤とは、特定波長の光照射に
より着色するか、または発泡し樹脂を白濁させるような
機能を有するものである。例えば （イ）光脱窒素（窒素発泡性）化合物、例えばナフトキ
ノンジアジド、アセチルアセトンジアジド、アセチル酢
酸スルホン酸ジアジド （ロ）ホトクロミズム化合物、例えばスピロラン系ジヒ
ドロインドリジン 等が挙げられる。Here, the colorant has a function of coloring or foaming by irradiation with light of a specific wavelength to make the resin cloudy. For example, (a) a photodenitrification (nitrogen foaming) compound, for example, naphthoquinonediazide, acetylacetonediazide, acetylacetatesulfonic acid diazide, (b) a photochromic compound, for example, a spiroran-based dihydroindolizine and the like.
【００１１】また、樹脂自体に着色または変色機能を付
与したものとしては、例えば （ハ）光硬化の際白濁する樹脂、例えばエポキシアクリ
レート、ウレタンアクリレート、ビニルピロリドン等に
ジシクロペンテニルエチルアクリレートおよび光重合開
始剤を添加したものが挙げられる。Examples of the resin which has a coloring or discoloring function include: (c) a resin which becomes opaque upon photocuring, such as epoxy acrylate, urethane acrylate, vinylpyrrolidone, etc .; Those to which an initiator is added may be mentioned.
【００１２】本発明の混合樹脂を硬化し、一部を選択的
に着色させる方法としては、分光感度が異なる光重合開
始剤および重合形式が異なる樹脂、例えば図１に示すよ
うな分光感度を有する光重合開始剤（Ａ，Ｂ）をそれぞ
れ含有する光カチオン重合系樹脂Ａ′と光ラジカル重合
系樹脂Ｂ′との二種よりなる混合樹脂を用いればよい。
即ち、上記それぞれの樹脂に含有させた光重合開始剤Ａ
およびＢにより、波長λ１の光が照射された部分ではカ
チオン重合のみが起こって樹脂Ａ′のみが硬化し、波長
λ２の光が照射された部分ではラジカル重合とカチオン
重合の双方が起り樹脂Ａ′、Ｂ′をともに硬化する。As a method of curing the mixed resin of the present invention and selectively coloring a part thereof, a photopolymerization initiator having a different spectral sensitivity and a resin having a different polymerization form, for example, having a spectral sensitivity as shown in FIG. It is sufficient to use a mixed resin composed of two kinds of a cationic photopolymerizable resin A 'and a photoradical polymerizable resin B' each containing a photopolymerization initiator (A, B).
That is, the photopolymerization initiator A contained in each of the above resins
By and B, only the resin A 'had occurred only cationic polymerization in the light is irradiated portion of the wavelength lambda 1 is cured, a portion where the light of the wavelength lambda 2 is irradiated occur both radical polymerization and cationic polymerization resins Both A 'and B' cure.
【００１３】このとき、前記（イ）、（ロ）および
（ハ）のいずれかの手段により着色機能を付与した光ラ
ジカル重合系樹脂を樹脂Ｂ′として使用し、波長λ2を
着色反応を生起しうる範囲で適切に選択して光照射すれ
ば、樹脂Ｂ′の照射部のみを着色することができる。ま
た、前記（イ）または（ロ）の着色剤を光ラジカル重合
系樹脂または光カチオン重合系樹脂に添加し、かつそれ
ぞれの樹脂に添加した重合開始剤の分光感度と着色剤の
分光感度との間に差を設ければ、樹脂への選択的な着色
が可能となる。At this time, a photo-radical polymerization resin to which a coloring function is imparted by any one of the above-mentioned means (a), (b) and (c) is used as the resin B ', and the wavelength λ 2 causes a coloring reaction. By irradiating light with an appropriate selection within a possible range, only the irradiated portion of the resin B 'can be colored. Further, the colorant of (a) or (b) is added to the radical photopolymerizable resin or the cationic photopolymerizable resin, and the spectral sensitivity of the polymerization initiator added to each resin and the spectral sensitivity of the colorant are determined. If a difference is provided, selective coloring of the resin becomes possible.
【００１４】例えば、図２に光重合開始剤ＡまたはＢと
着色剤Ｃとの波長に対する吸光度の関係を示すように、
それぞれの分光感度に差があれば、光重合開始剤のみの
分光感度領域λ1の光照射が施された部分では硬化のみ
が起こり着色または変色は生じないが、光重合開始剤お
よび着色剤双方の分光感度が重なった領域λ2の光照射
が施された部分は硬化されるとともに着色または変色さ
れる。For example, FIG. 2 shows the relationship between the absorbance of the photopolymerization initiator A or B and the colorant C with respect to the wavelength.
If there is a difference in the respective spectral sensitivity, both while in the light irradiation of the spectral sensitivity region lambda 1 of the photoinitiator alone is applied portion does not occur coloring or discoloration occurs only curing, photopolymerization initiator and colorant The light-irradiated portion of the region λ 2 where the spectral sensitivities overlap is cured and colored or discolored.
【００１５】このように、分光感度の異なる光重合開始
剤および着色剤または着色もしくは変色機能を有する樹
脂を選択し組合せ、光照射波長を適切に選択することに
より樹脂を複数色に色分けすることが可能となる。な
お、得られた立体造形物には、必要に応じて、光または
熱によりポストキュアーを実施してもよい。As described above, by selecting and combining photopolymerization initiators and colorants having different spectral sensitivities or resins having a coloring or discoloring function, and appropriately selecting the light irradiation wavelength, the resins can be classified into a plurality of colors. It becomes possible. The obtained three-dimensional structure may be post-cured by light or heat as necessary.
【００１６】本発明に使用される光カチオン重合系樹脂
としては、例えばノボラック型エポキシ化合物や脂環式
エポキシ化合物等が使用できる。ノボラック型エポキシ
化合物の市販品としては、例えば日本化薬（株）製ＥＯ
ＣＮ−１０２Ｓ、１０３、１０４Ｓ、１０２０、１０２
７、油化シェルエポキシ（株）製エピコート１８０Ｓ７
５等が挙げられる。脂環式エポキシ化合物の市販品とし
ては、例えばチバガイギー社製ＣＹ−１７５、１７７、
１７９、Ｕ．Ｃ．Ｃ．社製ＥＲＬ−４２３４、４２９
９、４２２１、４２０６等が挙げられる。As the cationic photopolymerizable resin used in the present invention, for example, a novolak type epoxy compound or an alicyclic epoxy compound can be used. Commercially available novolak epoxy compounds include, for example, EO manufactured by Nippon Kayaku Co., Ltd.
CN-102S, 103, 104S, 1020, 102
7. Yuko Shell Epoxy Co., Ltd. Epicoat 180S7
5 and the like. Commercially available alicyclic epoxy compounds include, for example, CY-175, 177 manufactured by Ciba-Geigy,
179, U.S.A. C. C. ERL-4234, 429
9, 4221, and 4206.
【００１７】本発明に使用される光ラジカル重合系樹脂
としては、例えばアクリレートまたはメタクリレート化
合物やスピロアセタールとアクリル基またはメタクリル
基を有するスピラル化合物等が使用できる。アクリレー
トまたはメタクリレート化合物の市販品としては、例え
ば東亜合成化学社製アロニックスＭ５７００、Ｍ６１０
０、Ｍ８０３０、Ｍ１５２、Ｍ２０５、Ｍ２１５、Ｍ３
１５、Ｍ３２５、Ｍ４００、Ｍ４０５、Ｍ７２００、新
中村化学工業社製ＮＫエステルＡＢＰＥ−４、Ｕ−４Ｈ
Ａ、ＣＢ−１、ＣＢＸ−１、日本化薬社製カヤラドＲ６
０４、ＤＰＣＡ−３０、ＤＰＣＡ−６０、カヤマーＰＭ
−１、ＰＭ−２、サンノブコ社製フォトマー４０６１、
５００７、昭和高分子社製リポキシＶＲ６０、ＶＲ９
０、ＳＰ１５０９、大阪有機社製ビスコート５４０等が
挙げられる。スピロアセタールとアクリル基またはメタ
クリル基を有するスピラル化合物の市販品としては、例
えば昭和高分子社製スピラックＥ−４０００Ｘ、Ｕ３０
００等が挙げられる。As the radical photopolymerizable resin used in the present invention, for example, an acrylate or methacrylate compound or a spiral compound having spiroacetal and an acryl or methacryl group can be used. Commercially available acrylate or methacrylate compounds include, for example, Aronix M5700 and M610 manufactured by Toa Gosei Chemical Co., Ltd.
0, M8030, M152, M205, M215, M3
15, M325, M400, M405, M7200, NK ester ABPE-4, U-4H manufactured by Shin-Nakamura Chemical Co., Ltd.
A, CB-1, CBX-1, Nippon Kayaku Co., Ltd. Kayarad R6
04, DPCA-30, DPCA-60, KAYAMA PM
-1, PM-2, Sannobuko photomer 4061,
5007, Lipoxy VR60, VR9 manufactured by Showa Polymer Co., Ltd.
0, SP1509, Viscoat 540 manufactured by Osaka Organic Co., Ltd., and the like. Commercial products of a spiral compound having a spiroacetal and an acrylic or methacrylic group include, for example, Spirac E-4000X, U30 manufactured by Showa Polymer Co., Ltd.
00 and the like.
【００１８】本発明に使用される光ラジカル重合開始剤
としては、例えばベンゾフェノン化合物等が使用でき
る。該化合物の市販品として、例えばチバガイギー社製
イルガキュアー１８４、６５１、９０７、メルク社製ダ
ロキュアー１１７３、１１１６、２９５９等が挙げられ
る。本発明に使用される光カチオン重合開始剤として
は、例えばメタロセン化合物やスルホニウム塩等が使用
できる。メタロセン化合物の市販品としては、例えばチ
バガイギー社製イルガキュアー２６１等が挙げられる。
スルホニウム塩の市販品としては、例えば旭電化社製の
オプトマーＳＰ−１００、ＳＰ−１７０等が挙げられ
る。As the photoradical polymerization initiator used in the present invention, for example, a benzophenone compound or the like can be used. Commercially available products of the compound include, for example, Irgacure 184, 651, 907 manufactured by Ciba-Geigy, and Darocure 1173, 1116, 2959 manufactured by Merck. Examples of the cationic photopolymerization initiator used in the present invention include metallocene compounds and sulfonium salts. Commercially available metallocene compounds include, for example, Irgacure 261 manufactured by Ciba-Geigy.
Commercially available sulfonium salts include, for example, Optomer SP-100 and SP-170 manufactured by Asahi Denka Co., Ltd.
【００１９】また、樹脂を露光するための光源は、樹脂
を硬化および着色または変色し得る波長を選択できるも
のであればよく、例えばレーザ光、高圧水銀ランプの平
行光等が挙げられる。但し、立体モデル製造装置の光源
は、少なくとも選択波長に対応する光の波長を制御部か
ら任意に選択できることが必要で、例えば、色素レーザ
や複数レーザ発振装置による波長の選択、高圧水銀ラン
プ光のフィルター切り替え等による波長の選択等が可能
であることが必要となる。また、高圧水銀ランプの平行
光を光源として使用する場合には、光硬化性樹脂を２次
元パターニング露光するためのマスクやシャッター等を
使用する必要がある。The light source for exposing the resin may be any light source capable of selecting a wavelength at which the resin can be cured and colored or discolored. Examples thereof include laser light and parallel light from a high-pressure mercury lamp. However, the light source of the three-dimensional model manufacturing apparatus needs to be able to arbitrarily select at least the wavelength of light corresponding to the selected wavelength from the control unit. For example, selection of a wavelength by a dye laser or a plurality of laser oscillators, It is necessary to be able to select a wavelength by switching a filter or the like. When parallel light from a high-pressure mercury lamp is used as a light source, it is necessary to use a mask, a shutter, and the like for performing two-dimensional patterning exposure of the photocurable resin.
【００２０】[0020]
【実施例】以下に本発明を実施例により具体的に説明す
るが、本発明はこれらに限定されるものではない。EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.
【００２１】実施例１ 光ラジカル重合系樹脂と光カチオン重合系樹脂を重量比
１：１に混合した光硬化性樹脂を使用した。光ラジカル
重合系樹脂の組成はエポキシアクリレート（大阪有機社
製ビスコート５４０）４０重量部、ウレタンアクリレー
ト３０重量部、ビニルピロリドン１０重量部、ジシクロ
ペンテニルエチルアクリレート１０重量部、光重合開始
剤（チバガイギー社製イルガキュア−３６９）１０重量
部であった。但し、ウレタンアクリレートは下記の構造
を有する。 ＨＥＡ−ＴＤＩ−ＰＰＧ−ＴＤＩ−ＨＥＡ 注）ＨＥＡ；ヒドロキシエチルアクリレート ＴＤＩ；２，４−トリレンジイソシアネート ＰＰＧ；ポリプロピレングリコール 分子量４０００ なお、光ラジカル重合系樹脂は、硬化して白濁する機能
を有する。また、光カチオン重合系樹脂の組成は脂環式
エポキシ樹脂（チバガイギー社製アラルダイト ＣＹ
１７９）７０重量部と光重合開始剤（チバガイギー社製
イルガキュア−２６１）１０重量部である。光カチオン
重合開始剤およびラジカル重合開始剤の分光感度はそれ
ぞれ図３および図４に示す特性を有する。モデリングを
行った装置の概略を図５に示す。モデリングは、従来の
３次元立体モデル製造装置に光源として２波長（３６８
ｎｍ、５１４ｎｍ）のＡｒレーザを選択できる装置を使
用し、ＣＡＤで設計した図６に示す立体モデル６１の製
作を行った。図６中のブロック部６２はカチオン重合開
始剤と光ラジカル重合開始剤との分光感度が重なる領域
のＡｒレーザ（３６８ｎｍ）で露光し、その他の部分は
カチオン重合開始剤のみの分光感度領域のＡｒレーザ
（５１４ｎｍ）で露光した。その結果、図７に示すよう
にＡｒレーザ（３６８ｎｍ）で露光硬化した部分７２は
白色に着色し、他の部分７１は半透明の立体モデルが得
られた。Example 1 A photocurable resin obtained by mixing a photoradical polymerization resin and a photocation polymerization resin in a weight ratio of 1: 1 was used. The composition of the photo-radical polymerization resin is 40 parts by weight of epoxy acrylate (Viscoat 540 manufactured by Osaka Organic Co., Ltd.), 30 parts by weight of urethane acrylate, 10 parts by weight of vinylpyrrolidone, 10 parts by weight of dicyclopentenylethyl acrylate, and a photopolymerization initiator (Ciba-Geigy) Irgacure-369) was 10 parts by weight. However, urethane acrylate has the following structure. HEA-TDI-PPG-TDI-HEA Note) HEA; hydroxyethyl acrylate TDI; 2,4-tolylene diisocyanate PPG; polypropylene glycol, molecular weight 4000 The photo-radical polymerization resin has a function of curing and clouding. The composition of the cationic photopolymerizable resin is an alicyclic epoxy resin (araldite CY manufactured by Ciba-Geigy).
179) 70 parts by weight and 10 parts by weight of a photopolymerization initiator (Irgacure-261 manufactured by Ciba Geigy). The spectral sensitivities of the cationic photopolymerization initiator and the radical polymerization initiator have the characteristics shown in FIGS. 3 and 4, respectively. FIG. 5 shows an outline of the apparatus that performed the modeling. Modeling is performed by using a conventional three-dimensional solid model manufacturing apparatus with two wavelengths (368
Using a device capable of selecting an Ar laser of (nm, 514 nm), a three-dimensional model 61 shown in FIG. 6 designed by CAD was manufactured. 6 is exposed by an Ar laser (368 nm) in a region where the spectral sensitivities of the cationic polymerization initiator and the photo-radical polymerization initiator overlap, and the other portions are Ar regions in the spectral sensitivity region of only the cationic polymerization initiator. Exposure was performed with a laser (514 nm). As a result, as shown in FIG. 7, a portion 72 exposed and cured by an Ar laser (368 nm) was colored white, and the other portion 71 was a translucent three-dimensional model.
【００２２】実施例２ 光硬化性樹脂として脂環式エポキシ樹脂（チバガイギー
社製アラルダイト ＣＹ １７９）７０重量部、光重合
開始剤（チバガイギー社製イルガキュア−２６１）１０
重量部、着色剤（窒素発泡剤）としてｏ−ナフトキノン
ジアジド−５−スルホン酸ナトリウム１０重量部および
ジエチレングリコールジメチルエーテル１０重量部から
なる光カチオン重合系樹脂を使用した。光カチオン重合
開始剤と着色剤の分光感度特性はそれぞれ図３および図
８に示す特性を有する。モデリングは、実施例１で使用
した３次元立体モデルの製造装置を使用し、ＣＡＤで設
計した図９に示す立体モデル９１の製作を行った。図９
中のブロック部９２は光カチオン重合剤と着色剤との分
光感度が重なる領域のＡｒレーザ（３６８ｎｍ）で露光
し、その他の部分は光カチオン重合開始剤のみの分光感
度領域のＡｒレーザ（５１４ｎｍ）で露光した。その結
果、図１０に示すようにＡｒレーザ（３６８ｎｍ）で露
光硬化した部分１２は発泡し白色に着色し、他の部分１
１は赤い半透明の立体モデルが得られた。Example 2 70 parts by weight of an alicyclic epoxy resin (Araldite CY179 manufactured by Ciba-Geigy) and 10 parts of a photopolymerization initiator (Irgacure-261 manufactured by Ciba-Geigy) as a photocurable resin.
A cationic photopolymerizable resin comprising 10 parts by weight of sodium o-naphthoquinonediazide-5-sulfonate and 10 parts by weight of diethylene glycol dimethyl ether as a coloring agent (nitrogen blowing agent) was used. The spectral sensitivity characteristics of the cationic photopolymerization initiator and the colorant have the characteristics shown in FIGS. 3 and 8, respectively. For the modeling, the three-dimensional model 91 shown in FIG. 9 designed by CAD was manufactured using the three-dimensional three-dimensional model manufacturing apparatus used in Example 1. FIG.
The middle block portion 92 is exposed with an Ar laser (368 nm) in a region where the spectral sensitivities of the photocationic polymerization agent and the colorant overlap, and the other portion is an Ar laser (514 nm) in a spectral sensitivity region of only the photocationic polymerization initiator. Exposure. As a result, as shown in FIG. 10, the portion 12 exposed and cured by the Ar laser (368 nm) foams and is colored white, and the other portion 1
1 was a red translucent three-dimensional model.
【００２３】[0023]
【発明の効果】本発明によれば、立体モデルの硬化時
に、その一部または全部を任意に着色または変色可能で
ある。そして、複雑な内部構造を有するものでも外部よ
り明瞭に識別することができる。According to the present invention, a part or all of the three-dimensional model can be arbitrarily colored or discolored when the three-dimensional model is cured. And even those having a complicated internal structure can be clearly identified from the outside.
【図１】光カチオン重合開始剤（Ａ）と光ラジカル重合
開始剤（Ｂ）とのそれぞれの分光感度例を示す図であ
る。FIG. 1 is a diagram illustrating examples of spectral sensitivities of a photocationic polymerization initiator (A) and a photoradical polymerization initiator (B).
【図２】光重合開始剤（ＡまたはＢ）と着色剤Ｃとのそ
れぞれの分光感度例を示す図である。FIG. 2 is a diagram illustrating an example of spectral sensitivity of a photopolymerization initiator (A or B) and a colorant C.
【図３】実施例１および２で使用した光カチオン重合開
始剤の分光感度を示す図である。FIG. 3 is a diagram showing the spectral sensitivity of the cationic photopolymerization initiator used in Examples 1 and 2.
【図４】実施例１で使用した光ラジカル重合開始剤の波
長に対する分子吸光係数を示す図である。FIG. 4 is a diagram showing the molecular extinction coefficient with respect to the wavelength of the photoradical polymerization initiator used in Example 1.
【図５】実施例１で使用した装置の概略を示す図であ
る。FIG. 5 is a diagram schematically showing an apparatus used in Example 1.
【図６】実施例１のＣＡＤで設計した立体モデルを示す
透視図である。FIG. 6 is a perspective view showing a three-dimensional model designed by CAD according to the first embodiment.
【図７】実施例１で得られた立体モデルを示す透視図で
ある。FIG. 7 is a perspective view showing a three-dimensional model obtained in Example 1.
【図８】実施例２で使用した着色剤の分光感度を示す図
である。FIG. 8 is a view showing the spectral sensitivity of a colorant used in Example 2.
【図９】実施例２のＣＡＤで設計した立体モデルを示す
透視図である。FIG. 9 is a perspective view showing a three-dimensional model designed by CAD according to the second embodiment.
【図１０】実施例２で得られた立体モデルを示す透視図
である。FIG. 10 is a perspective view showing a three-dimensional model obtained in Example 2.
Ａ．……光カチオン重合開始剤 Ｂ．……光ラジカル重合開始剤 Ｃ．……着色剤 ５１……ＣＡＤデータ ５２……コントローラ ５３……Ａｒレーザ（３６８ｎｍ） ５４……Ａｒレーザ（５１４ｎｍ） ５５……ミラー ５６……光硬化性樹脂 ６１……立体モデル ６２……ブロック部 ７１……半透明部 ７２……着色部 ９１……立体モデル ９２……ブロック部 １１……赤の半透明部 １２……着色部 A. .... Photocationic polymerization initiator B. ... Photoradical polymerization initiator C.I. ... Colorant 51... CAD data 52... Controller 53... Ar laser (368 nm) 54... Ar laser (514 nm) 55... Mirror 56... 71 translucent part 72 colored part 91 three-dimensional model 92 block part 11 red translucent part 12 colored part
Claims (2)
る一種の光重合開始剤と、光硬化性樹脂と、光重合開始
剤ではない着色剤とを含有する光硬化性樹脂組成物を用
い、 （ｉ）該光重合開始剤と該着色剤とに共通する吸収波長
の光を該光硬化性樹脂組成物の選択領域に照射して該光
硬化性樹脂組成物の該選択領域を硬化および着色する工
程と、 （ｉｉ）該光重合開始剤の吸収波長であって該着色剤の
吸収波長でない波長の光を該光硬化性樹脂組成物に照射
して、該光硬化性樹脂組成物を硬化するが着色しない工
程とを含むことを特徴とする、一部が着色された立体モ
デルの製造方法。1. A photocurable resin composition containing at least two kinds of photopolymerization initiators having different absorption wavelengths, a photocurable resin, and a colorant that is not a photopolymerization initiator, wherein (i) A) a step of irradiating a selected region of the photocurable resin composition with light having an absorption wavelength common to the photopolymerization initiator and the colorant to cure and color the selected region of the photocurable resin composition; And (ii) irradiating the photocurable resin composition with light having a wavelength that is the absorption wavelength of the photopolymerization initiator but is not the absorption wavelength of the colorant, thereby curing the photocurable resin composition. A method of producing a partially colored three-dimensional model, comprising a step of not coloring.
硬化性樹脂にそれぞれ対応しそして互いに異なる吸収波
長を有する少なくとも二種の光重合開始剤とを含有する
光硬化性樹脂組成物であって、該光硬化性樹脂の少なく
とも一種が硬化の際着色または変色する光硬化性樹脂で
あり、少なくとも一種が硬化の際着色も変色もしない光
硬化性樹脂である該光硬化性樹脂組成物を用い、 （ｉ）該硬化の際着色または変色する光硬化性樹脂に対
応する光重合開始剤の吸収波長の光を該光硬化性樹脂組
成物の選択領域に照射して該樹脂組成物の該選択領域を
硬化および着色または変色させる工程と、 （ｉｉ）該硬化の際着色も変色もしない光硬化性樹脂に
対応する光重合開始剤の吸収波長の光を該光硬化性樹脂
組成物に照射して、該光硬化性樹脂組成物を硬化するが
着色しない工程とを含むことを特徴とする、一部が着色
または変色された立体モデルの製造方法。2. A photocurable resin composition comprising at least two photocurable resins and at least two photopolymerization initiators respectively corresponding to the photocurable resins and having mutually different absorption wavelengths. The photocurable resin composition, wherein at least one of the photocurable resins is a photocurable resin that is colored or discolored when cured, and at least one is a photocurable resin that is not colored or discolored when cured. And (i) irradiating a selected region of the photocurable resin composition with light having an absorption wavelength of a photopolymerization initiator corresponding to the photocurable resin that is colored or discolored during the curing. Curing and coloring or discoloring the selected area; and (ii) applying, to the photocurable resin composition, light having an absorption wavelength of a photopolymerization initiator corresponding to the photocurable resin that does not discolor or discolor during the curing. Irradiate the photocurable resin set Curing the object is characterized in that it comprises a step which is not colored, the manufacturing method of the part of which is colored or discolored solid model.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01903392A JP3200912B2 (en) | 1992-02-04 | 1992-02-04 | 3D model manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01903392A JP3200912B2 (en) | 1992-02-04 | 1992-02-04 | 3D model manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05212804A JPH05212804A (en) | 1993-08-24 |
| JP3200912B2 true JP3200912B2 (en) | 2001-08-20 |
Family
ID=11988135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01903392A Expired - Lifetime JP3200912B2 (en) | 1992-02-04 | 1992-02-04 | 3D model manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3200912B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3882147B2 (en) * | 1995-09-09 | 2007-02-14 | バンティコ リミテッド | Method for producing a polymer layer having selectively colored regions |
| AU757339B2 (en) * | 1998-07-25 | 2003-02-20 | Vantico Limited | Colour changing composition and colouring polymeric articles made therefrom |
| JP4493814B2 (en) * | 2000-07-28 | 2010-06-30 | ナブテスコ株式会社 | Method and apparatus for producing colored shaped article made of curable resin |
| US20040170923A1 (en) * | 2003-02-27 | 2004-09-02 | 3D Systems, Inc. | Colored stereolithographic resins |
| WO2023026905A1 (en) * | 2021-08-25 | 2023-03-02 | ナガセケムテックス株式会社 | Resin composition for three-dimensional photoshaping |
| JP7224557B1 (en) * | 2021-08-25 | 2023-02-17 | ナガセケムテックス株式会社 | Three-dimensional stereolithography resin composition |
-
1992
- 1992-02-04 JP JP01903392A patent/JP3200912B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05212804A (en) | 1993-08-24 |
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